Crystalline metallophosphates, their method of preparation, and use

ABSTRACT

A new family of crystalline microporous metallophosphates designated AlPO-78 has been synthesized. These metallophosphates are represented by the empirical formula 
       R +   r M m   2+ EP x Si y O z    
     where R is an organoammonium cation, M is a framework metal alkaline earth or transition metal of valence +2, and E is a trivalent framework element such as aluminum or gallium. The AlPO-78 compositions are characterized by a new unique ABC-6 net structure, and have catalytic properties suitable for carrying out various hydrocarbon conversion processes, as well as characteristics suitable for the efficient adsorption of water vapor in a variety of applications, such as adsorption heat pumps.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from Provisional Application No.62/538,403 filed Jul. 28, 2017, the contents of which cited applicationare hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

This invention relates to a novel family of metallophosphates,collectively designated AlPO-78. They are represented by the empiricalformula:

R⁺ _(r)M_(m) ²⁺EP_(x)Si_(y)O_(z)

where M is a divalent framework metal such as magnesium or zinc, R is anorganoammonium cation, and E is a trivalent framework element such asaluminum or gallium.

Classes of molecular sieves include crystalline aluminophosphate,silicoaluminophosphate, or metalloaluminophosphate compositions whichare microporous and which are formed from corner sharing AlO_(4/2) andPO_(4/2) tetrahedra. In 1982, Wilson et al. first reportedaluminophosphate molecular sieves, the so-called AlPOs, which aremicroporous materials that have many of the same properties as zeolites,although they do not contain silica (see U.S. Pat. No. 4,310,440).Subsequently, charge was introduced to the neutral aluminophosphateframeworks via the substitution of SIO_(4/2) tetrahedra for PO_(4/2) ⁺tetrahedra to produce the SAPO molecular sieves as described by Lok etal. (see U.S. Pat. No. 4,440,871). Another way to introduce frameworkcharge to neutral aluminophosphates is to substitute [Me²⁺O_(4/2)]²⁻tetrahedra for AlO_(4/2) ⁻ tetrahedra, which yields the MeAPO molecularsieves (see U.S. Pat. No. 4,567,029). It is furthermore possible tointroduce framework charge on AlPO-based molecular sieves via thesimultaneous introduction of SiO_(4/2) and [M²⁺O_(4/2)]²⁻ tetrahedra tothe framework, giving MeAPSO molecular sieves (see U.S. Pat. No.4,973,785).

Numerous molecular sieves, both naturally occurring and syntheticallyprepared, are used in various industrial processes. Synthetically, thesemolecular sieves are prepared via hydrothermal synthesis employingsuitable sources of Si, Al, P, metals, and structure directing agentssuch as amines or organoammonium cations. The structure directing agentsreside in the pores of the molecular sieve and are largely responsiblefor the particular structure that is ultimately formed. These speciesmay balance the framework charge associated with silicon or other metalssuch as Zn or Mg in the aluminophosphate compositions, and can alsoserve as space fillers to stabilize the tetrahedral framework. Molecularsieves are characterized by having pore openings of uniform dimensions,having a significant ion exchange capacity, and being capable ofreversibly desorbing an adsorbed phase which is dispersed throughout theinternal voids of the crystal without significantly displacing any atomswhich make up the permanent molecular sieve crystal structure. Molecularsieves can be used as catalysts for hydrocarbon conversion reactions,which can take place on outside surfaces as well as on internal surfaceswithin the pore.

As stated above, molecular sieves are capable of reversibly adsorbingand desorbing certain molecules depending on the adsorbate's size andthe molecular sieve's internal pore structure. There are manyapplications where it is desired to adsorb water vapor, preferably in areversible manner. One such application is an adsorption heat pump,which is a device that can be used to recover energy from exhaust orwaste heat. As such, adsorption heat pumps can be utilized to maximizeenergy efficiency in an environmentally friendly manner. Molecularsieves can be useful materials to act as water vapor adsorbents in anadsorption heat pump due to their high capacity for water vapor. Adescription of the use of adsorbents in adsorption heat pumps can befound in U.S. Pat. No. 8,323,747, incorporated by reference herein inits entirety.

The type of molecular sieves used in adsorption heat pumps must meetcertain requirements for optimal performance. A high overall capacityfor water vapor is important, but most critically, they should fullydesorb all adsorbed water at no greater than 100° C. Otherwise, too muchheat must be applied to fully remove the adsorbed water from themicropores (i.e., the regeneration temperature is too high), thusrequiring too high of an energy input. The majority of aluminosilicates(i.e., zeolites) have rapid uptake of water vapor at very low pressures(P/P₀), which conversely leads to an unacceptably high regenerationtemperature, despite a high overall capacity for water vapor.Aluminophosphates and silicoaluminophosphates have been shown to havemore favorable adsorption characteristics for water vapor (see, forexample, M. F. de Lange et al. CHEM. REV. 115, 12205 (2015); H. vanHeyden et al. APPL. THERM. ENG. 29, 1514 (2009). In particular, thematerials SAPO-34 and SAPO-5 (zeotypes CHA and AFI, respectively) havebeen shown to have particular utility as adsorbent materials inadsorption heat pumps (see U.S. Pat. Nos. 7,422,993 and 9,517,942).

SUMMARY OF THE INVENTION

As stated, the present invention relates to a new family ofmetallophosphate molecular sieves, collectively designated AlPO78.Accordingly, one embodiment of the invention is a microporouscrystalline material having a three-dimensional framework of at leastEO_(4/2) ⁻ and PO_(4/2) ⁺ tetrahedral units and optionally, at least oneof [M²⁺O_(4/2)]²⁻ and SiO_(4/2) tetrahedral units and an empiricalcomposition in the as-synthesized form and anhydrous basis expressed byan empirical formula of:

R⁺ _(r)M_(m) ²⁺EP_(x)Si_(y)O_(z)

where M is at least one metal cation of valence +2 selected from thegroup consisting of Be²⁺, Mg²⁺, Zn²⁺, Co²⁺, Mn²⁺, Fe²⁺, Ni²⁺, “m” is themole ratio of M to E and varies from 0 to about 1.0, and R is anorganoammonium cation. “r” is the mole ratio of R to E and has a valueof about 0.1 to about 2.0, E is a trivalent element selected from thegroup consisting of aluminum, gallium, iron, boron and mixtures thereof,“x” is mole ratio of P to E and varies from 0.5 to about 2.0, “y” is themole ratio of Si to E and varies from 0 to about 1.0, and “z” is themole ratio of O to E and has a value determined by the equation:

z=(2·m+r+3+5·x+4·y)/2

The invention is characterized in that it has the x-ray diffractionpattern having at least the d-spacings and intensities set forth inTable 1:

TABLE 1 2-Theta d(Å) Intensity 7.88-7.98 11.21-11.07 m-s 8.15-8.5010.84-10.39 m-s 8.82-9.05 10.01-9.76  s 9.67-9.96 9.14-8.87 s-vs10.58-10.81 8.35-8.17 m 10.92-11.71 8.09-7.55 m-s 13.21-13.67 6.69-6.47s 14.10-14.54 6.27-6.08 s-vs 15.48-16.02 5.72-5.53 m 16.05-16.245.52-5.45 s 16.44-16.81 5.39-5.28 m 16.87-17.01 5.25-5.21 m-s17.19-17.43 5.15-5.08 s 17.78-18.46 4.98-4.80 s-vs 18.73-19.22 4.73-4.61vw-w 19.48-19.86 4.55-4.47 w-m 20.47-20.96 4.33-4.23 s 21.00-21.454.23-4.14 m-s 21.52-21.73 4.12-4.08 m-s 21.88-22.10 4.06-4.02 s22.15-22.42 4.01-3.96 m-s 22.52-22.95 3.94-3.87 w-m 23.14-23.523.84-3.78 w-m 23.58-23.71 3.77-3.75 s 23.75-24.01 3.74-3.70 w-m24.75-24.93 3.59-3.57 w-m 25.01-25.47 3.56-3.49 vs 26.15-26.31 3.40-3.38w-m 26.37-26.54 3.38-3.35 m 26.78-27.02 3.33-3.30 w-m 27.11-27.403.29-3.25 m 28.39-28.86 3.14-3.09 w-m 29.22-29.65 3.05-3.01 m30.60-30.95 2.92-2.89 w-m 31.62-31.93 2.83-2.80 w-m 31.97-32.282.80-2.77 w-s 32.44-32.89 2.76-2.72 w-m 33.19-33.40 2.70-2.68 vw-w33.51-33.82 2.67-2.65 w-m 34.72-35.08 2.58-2.55 vw-w

Another embodiment of the invention is a microporous crystallinematerial having a three-dimensional framework of at least EO_(4/2) ⁻ andPO_(4/2) ⁺ tetrahedral units and optionally, at least one of[M²⁺O_(4/2)]²⁻ and SiO_(4/2) tetrahedral units and an empiricalcomposition in the calcined form and anhydrous basis expressed by anempirical formula of:

H_(w)M_(m) ²⁺EP_(x)Si_(y)O_(z)

where “m”, “x”, “y” are as described above, H is a proton, “w” is themole ratio of H to E and varies from 0 to 2.5, and “z” is the mole ratioof O to E and has a value determined by the equation:

z=(w+2·m+3+5·x+4·y)/2

and the invention is characterized in that it has the x-ray diffractionpattern having at least the d-spacings and intensities set forth inTable 2:

TABLE 2 2-Theta d(Å) Intensity 8.02-8.12 11.01-10.88 w 8.40-8.5110.51-10.38 m 8.63-8.73 10.23-10.12 w-m 9.78-9.89 9.03-8.93 m-s10.70-10.81 8.26-8.17 m-s 12.83-12.95 6.89-6.82 vw 13.71-13.86 6.45-6.38vs 14.00-14.13 6.32-6.26 m-s 16.16-16.64 5.48-5.32 vw-w 16.92-17.055.23-5.19 vw-w 17.44-17.56 5.08-5.04 m 17.79-17.93 4.98-4.94 m-s19.68-19.89 4.51-4.46 w 20.43-20.61 4.34-4.30 w-m 21.17-21.35 4.19-4.16w-m 21.81-21.99 4.07-4.04 m-s 22.15-22.53 4.01-3.94 m-s 22.55-22.743.94-3.91 w-m 23.95-24.25 3.71-3.67 m-s 24.57-24.79 3.62-3.59 m-s25.87-26.31 3.44-3.38 w-m 26.49-26.71 3.36-3.33 m 27.40-27.88 3.25-3.20m-s 28.32-28.52 3.15-3.13 m-s 28.85-29.02 3.09-3.07 vw-w 29.40-29.633.03-3.01 w-m 29.71-29.93 3.00-2.98 vw 30.28-30.44 2.95-2.93 vw-w31.21-31.38 2.86-2.85 vw-w 32.18-32.50 2.79-2.75 w-m 32.65-32.922.74-2.72 w-m 33.00-33.15 2.71-2.70 w-m 34.25-34.41 2.61-2.60 vw-w35.16-35.35 2.55-2.54 w-m

Another embodiment of the invention is a process for preparing thecrystalline microporous metallophosphate molecular sieve describedabove. The process comprises forming a reaction mixture containingreactive sources of R, E, P, one or both of M and Si, and heating thereaction mixture at a temperature of about 60° C. to about 200° C. for atime sufficient to form the molecular sieve, the reaction mixture havinga composition expressed in terms of mole ratios of the oxides of:

aR₂O:bMO:E₂O₃:cP₂O₅:dSiO₂:eH₂O

where “a” has a value of about 0.75 to about 12, “b” has a value ofabout 0 to about 2, “c” has a value of about 0.5 to about 8, “d” has avalue of about 0 to about 4, and “e” has a value from 30 to 1000.

Yet another embodiment of the invention is a hydrocarbon conversionprocess using the above-described molecular sieve as a catalyst. Theprocess comprises contacting at least one hydrocarbon with the molecularsieve at conversion conditions to generate at least one convertedhydrocarbon.

Still another embodiment of the invention is an adsorption process usingthe crystalline AlPO-78 material. The process may involve the adsorptionand desorption of water vapor over AlPO-78 in an adsorption heatpump-type apparatus. Separation of molecular species can be based eitheron the molecular size (kinetic diameter) or on the degree of polarity ofthe molecular species. Removing contaminants may be by ion exchange withthe molecular sieve.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a scanning electron microscope (SEM) image of an exemplaryAlPO-78 material according to an embodiment described herein.

FIG. 2 is a graph showing water adsorption isotherms of exemplaryAlPO-78 materials along with comparative example materials. Details arediscussed in Example 9.

FIG. 3 is an x-ray diffraction pattern of an exemplary AlPO-78 materialin the as-synthesized form.

FIG. 4 is an x-ray diffraction pattern of an exemplary AlPO-78 materialin the calcined form.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have prepared a family of metallophosphate materials whosetopological structure is unique. In their paper “Enumeration of4-connected 3-dimensional nets and classification of frameworksilicates: the infinite set of ABC-6 nets; the Archimedean and σ-relatednets,” Smith and Bennett state “To a first approximation, all silicatesbelonging to the ABC-6net family have x-ray diffraction patterns whichcan be indexed on a hexagonal prismatic unit cell with latticeparameters a ˜13.0+0.3 Å and c˜p×(2.6±0.1 Å)” (see AMERICANMINERALOGIST, 66, 777-788 (1981)). This finding has subsequently beenconfirmed by others (see, for example, D. Xie et al. J. AM. CHEM. SOC.135, 10519 (2013)) as the ABC-6 family has expanded.

One particular composition of AlPO-78 indexes on a unit cell withhexagonal axes with lattice parameters a=12.768 Å and c=60.825 Å, whichis suggests an ABC-6 net structure with the stacking sequence repeatingevery 24 layers along the c-axis (p=60.825/2.5=24.33). This is the firstknown example of an ABC-6 net structure with 24-layer repeats, and wouldbe the largest repeat unit ever reported in a synthetic ABC-6 netmolecular sieve. Hence the topology of AlPO-78 family of materials isunique. The instant microporous crystalline material (AlPO-78) has anempirical composition in the as-synthesized form and on an anhydrousbasis expressed by the empirical formula:

R⁺ _(r)M_(m) ²⁺EP_(x)Si_(y)O_(z)

where M is at least one framework divalent cation and is selected fromthe group consisting of alkaline earth and transition metals. Specificexamples of the M cations include but are not limited to beryllium,magnesium, cobalt (II), manganese, zinc, iron (II), nickel and mixturesthereof. R is an organoammonium cation. “r” is the mole ratio of R to Eand varies from about 0.1 to about 2.0. The value of “m” is the moleratio of M to E and varies from 0 to about 1.0, “x” is mole ratio of Pto E and varies from 0.5 to about 2.0. The ratio of silicon to E isrepresented by “y” which varies from about 0 to about 1.0. E is atrivalent element which is tetrahedrally coordinated, is present in theframework, and is selected from the group consisting of aluminum,gallium, iron (III) and boron. Lastly, “z” is the mole ratio of O to Eand is given by the equation:

z=(2·m+r+3+5·x+4·y)/2.

Synthesis of molecular sieve materials often relies on the use oforganoamino or organoammonium templates known as organic structuredirecting agents (OSDAs). While simple OSDAs such astetramethylammonium, tetraethylammonium and tetrapropylammonium arecommercially available, oftentimes OSDAs are complicated molecules thatare difficult and expensive to synthesize. However, their importancelies in their ability to impart aspects of their structural features tothe molecular sieve to yield a desirable pore structure. For example,the use of1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane as OSDAhas been shown to allow synthesis of STA-7, an aluminophosphate basedmaterial of the SAV zeotype (Wright et.al. J. CHEM. SOC., Dalton Trans.,2000, 1243-1248); the use of4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (‘Kryptofix222’) led to the synthesis of AlPO₄-42 (Schreyeck et.al. MICRO. MESO.MATER. 1998, 22, 87-106); MAPO-35, a magnesium aluminophosphate materialwith the LEV topology, is disclosed in U.S. Pat. No. 4,567,029 in whichquinuclidine is employed as a structure directing agent; and in U.S.Pat. No. 4,973,785, the MeAPSO composition CoAPSO-35 is disclosed, whichcontains both cobalt and silicon in the framework in addition to Al andP and uses methylquinuclidine as the structure directing agent.

The art clearly shows that use of complex organoammonium SDAs oftenresults in new molecular sieve materials. However, the synthesis ofthese complicated organoammonium compounds is quite lengthy and requiresmany steps, often in an organic solvent, thereby hindering developmentof the new molecular sieve material. Frequently, even for simple,commercially available OSDAs, the OSDA is the most costly ingredientused in synthesizing molecular sieve materials. Consequently, it wouldbe economically advantageous to synthesize new molecular sieves fromeither commercially available organoammonium SDAs or SDAs which may bereadily synthesized from commercially available starting materials. Thishas recently been demonstrated in an elegant fashion using simpleaqueous chemistry to generate a novel family of organo-1-oxa-4-azoniumcyclohexane compounds (U.S. Pat. No. 9,522,896), derived frommorpholino-based compounds. The procedures described in U.S. Pat. No.9,522,896 can be extended to the family of piperidine-based compounds aswell. This procedure thereby allows the preparation of SDAs, such asunusual quaternary ammonium salts, from readily available startingreagents in a facile and practical manner. OSDAs prepared by the methodsof the present invention are in aqueous solution and do not pose odorand flashpoint concerns. The result is the unprecedented ability toremove the cooling step typically required in the preparation of in-situzeolite reaction mixtures and to avoid purification steps such asevaporation of organic solvent typically required in ex-situ preparationmethods. The obtained organoammonium bromide salt can be ion-exchanged,either by reaction with Ag₂O or by anion exchange resins to yield thehydroxide form of the organoammonium compound, or used as the halogensalt directly. Finally, the resultant organoammonium compound can beused for the synthesis of a zeolite or molecular sieve.

The microporous crystalline metallophosphate AlPO-78 is prepared by ahydrothermal crystallization of a reaction mixture prepared by combiningreactive sources of R, E, phosphorus, and one or both of M and silicon.A preferred form of the AlPO-78 materials is when E is Al. The sourcesof aluminum include but are not limited to aluminum alkoxides,precipitated aluminas, aluminum metal, aluminum hydroxide, aluminumsalts and alumina sols. Specific examples of aluminum alkoxides include,but are not limited to aluminum ortho sec-butoxide and aluminum orthoisopropoxide. Sources of phosphorus include, but are not limited to,orthophosphoric acid, phosphorus pentoxide, and ammonium dihydrogenphosphate. Sources of silica include but are not limited totetraethylorthosilicate, colloidal silica, and precipitated silica.Sources of the other E elements include but are not limited toorganoammonium borates, boric acid, precipitated gallium oxyhydroxide,gallium sulfate, ferric sulfate, and ferric chloride. Sources of the Mmetals include the halide salts, nitrate salts, acetate salts, andsulfate salts of the respective alkaline earth and transition metals. Ris an organoammonium cation prepared from the reaction of an aqueousmixture of a cyclic secondary amine and an organic dihalide. Specificexamples of cyclic secondary amines include, without limitation,piperidine, homopiperidine, pyrrolidine, and morpholine. Specificexamples of organic dihalides include, without limitation,1,4-dibromobutane, 1,5-dibromopentane, and 1,6-dibromohexane.

In one embodiment, the cyclic secondary amine is piperidine and theorganic dihalide is 1,4-dibromobutane. In another embodiment, the cyclicsecondary amine is piperidine and the organic dihalide is1,4-dibromopentane. In another embodiment, the cyclic secondary amine ispiperidine and the organic dihalide is 1,5-dibromopentane. In anotherembodiment, the cyclic secondary amine is pyrrolidine and the organicdihalide is 1,4-dibromobutane.

The reaction mixture containing reactive sources of the desiredcomponents can be described in terms of molar ratios of the oxides bythe formula:

aR₂O:bMO:E₂O₃:cP₂O₅:dSiO₂:eH₂O

where “a” has a value of about 0.75 to about 12, “b” has a value ofabout 0 to about 2, “c” has a value of about 0.5 to about 8, “d” has avalue of about 0 to about 4, and “e” has a value from 30 to 1000. Ifalkoxides are used, it is preferred to include a distillation orevaporative step to remove the alcohol hydrolysis products.

The reaction mixture is reacted at a temperature of about 60° C. toabout 200° C. and preferably from about 125° C. to about 175° C. for aperiod of about 1 day to about 21 days and preferably for a time ofabout 2 days to about 10 days in a sealed reaction vessel at autogenouspressure. The reaction vessel may be heated with stirring, heated whiletumbling, or heated quiescently. After crystallization is complete, thesolid product is isolated from the heterogeneous mixture by means suchas filtration or centrifugation, and then washed with deionized waterand dried in air at ambient temperature up to about 100° C. AlPO-78seeds can optionally be added to the reaction mixture in order toaccelerate the formation of the desired microporous composition.

The AlPO-78 aluminophosphate-based material, which is obtained from theabove-described process, is characterized by the x-ray followingdiffraction pattern, having at least the d-spacings and relativeintensities set forth in Table 1:

TABLE 1 2-Theta d(Å) Intensity 7.88-7.98 11.21-11.07 m-s 8.15-8.5010.84-10.39 m-s 8.82-9.05 10.01-9.76  s 9.67-9.96 9.14-8.87 s-vs10.58-10.81 8.35-8.17 m 10.92-11.71 8.09-7.55 m-s 13.21-13.67 6.69-6.47s 14.10-14.54 6.27-6.08 s-vs 15.48-16.02 5.72-5.53 m 16.05-16.245.52-5.45 s 16.44-16.81 5.39-5.28 m 16.87-17.01 5.25-5.21 m-s17.19-17.43 5.15-5.08 s 17.78-18.46 4.98-4.80 s-vs 18.73-19.22 4.73-4.61vw-w 19.48-19.86 4.55-4.47 w-m 20.47-20.96 4.33-4.23 s 21.00-21.454.23-4.14 m-s 21.52-21.73 4.12-4.08 m-s 21.88-22.10 4.06-4.02 s22.15-22.42 4.01-3.96 m-s 22.52-22.95 3.94-3.87 w-m 23.14-23.523.84-3.78 w-m 23.58-23.71 3.77-3.75 s 23.75-24.01 3.74-3.70 w-m24.75-24.93 3.59-3.57 w-m 25.01-25.47 3.56-3.49 vs 26.15-26.31 3.40-3.38w-m 26.37-26.54 3.38-3.35 m 26.78-27.02 3.33-3.30 w-m 27.11-27.403.29-3.25 m 28.39-28.86 3.14-3.09 w-m 29.22-29.65 3.05-3.01 m30.60-30.95 2.92-2.89 w-m 31.62-31.93 2.83-2.80 w-m 31.97-32.282.80-2.77 w-s 32.44-32.89 2.76-2.72 w-m 33.19-33.40 2.70-2.68 vw-w33.51-33.82 2.67-2.65 w-m 34.72-35.08 2.58-2.55 vw-w

The AlPO78 material may be calcined in either air or nitrogen to removethe occluded template. In one embodiment of the invention, the AlPO78 iscalcined at a temperature of at least 550° C. In another embodiment ofthe invention, the AlPO78 is calcined at a temperature of at least 600°C. The AlPO-78 is thermally stable upon calcination, and may becharacterized by the x-ray diffraction pattern, having at least thed-spacings and relative intensities set forth in Table 2 below:

TABLE 2 2-Theta d(Å) Intensity 8.02-8.12 11.01-10.88 w 8.40-8.5110.51-10.38 m 8.63-8.73 10.23-10.12 w-m 9.78-9.89 9.03-8.93 m-s10.70-10.81 8.26-8.17 m-s 12.83-12.95 6.89-6.82 vw 13.71-13.86 6.45-6.38vs 14.00-14.13 6.32-6.26 m-s 16.16-16.64 5.48-5.32 vw-w 16.92-17.055.23-5.19 vw-w 17.44-17.56 5.08-5.04 m 17.79-17.93 4.98-4.94 m-s19.68-19.89 4.51-4.46 w 20.43-20.61 4.34-4.30 w-m 21.17-21.35 4.19-4.16w-m 21.81-21.99 4.07-4.04 m-s 22.15-22.53 4.01-3.94 m-s 22.55-22.743.94-3.91 w-m 23.95-24.25 3.71-3.67 m-s 24.57-24.79 3.62-3.59 m-s25.87-26.31 3.44-3.38 w-m 26.49-26.71 3.36-3.33 m 27.40-27.88 3.25-3.20m-s 28.32-28.52 3.15-3.13 m-s 28.85-29.02 3.09-3.07 vw-w 29.40-29.633.03-3.01 w-m 29.71-29.93 3.00-2.98 vw 30.28-30.44 2.95-2.93 vw-w31.21-31.38 2.86-2.85 vw-w 32.18-32.50 2.79-2.75 w-m 32.65-32.922.74-2.72 w-m 33.00-33.15 2.71-2.70 w-m 34.25-34.41 2.61-2.60 vw-w35.16-35.35 2.55-2.54 w-m

The stable calcined AlPO-78 material can be characterized on ananhydrous basis by the empirical formula:

H_(w)M_(m) ²⁺EP_(x)Si_(y)O_(z)

where M is at least one metal cation of valence +2 selected from thegroup consisting of Be²⁺, Mg²⁺, Zn²⁺, Co²⁺, Mn²⁺, Fe²⁺, Ni²⁺, “m” is themole ratio of M to E and varies from 0 to about 1.0, H is a proton, w”is the mole ratio of H to E and varies from 0 to 2.5, E is a trivalentelement selected from the group consisting of aluminum, gallium, iron,boron and mixtures thereof, “x” is mole ratio of P to E and varies from0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0 toabout 1.0, and “z” is the mole ratio of O to E and has a valuedetermined by the equation:

z=(w+2·m+3+5·x+4·y)/2

The crystalline AlPO-78 materials of this invention can be used forseparating mixtures of molecular species, removing contaminants throughion exchange and catalyzing various hydrocarbon conversion processes.Separation of molecular species can be based either on the molecularsize (kinetic diameter) or on the degree of polarity of the molecularspecies.

The AlPO78 compositions of this invention can also be used as a catalystor catalyst support in various hydrocarbon conversion processes.Hydrocarbon conversion processes are well known in the art and includecracking, hydrocracking, alkylation of both aromatics and isoparaffin,isomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydration, dehydration,hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanol toolefins, methanation and syngas shift process. Specific reactionconditions and the types of feeds which can be used in these processesare set forth in U.S. Pat. Nos. 4,310,440, 4,440,871 and 5,126,308,which are incorporated by reference.

The AlPO-78 materials may also be used as a catalyst for the conversionof methanol to olefins. The methanol can be in the liquid or vapor phasewith the vapor phase being preferred. Contacting the methanol with theAlPO-78 catalyst can be done in a continuous mode or a batch mode with acontinuous mode being preferred. The amount of time that the methanol isin contact with the AlPO-78 catalyst must be sufficient to convert themethanol to the desired light olefin products. When the process iscarried out in a batch process, the contact time varies from about 0.001hrs to about 1 hr and preferably from about 0.01 hr to about 1.0 hr. Thelonger contact times are used at lower temperatures while shorter timesare used at higher temperatures. When the process is carried out in acontinuous mode, the Weight Hourly Space Velocity (WHSV) based onmethanol can vary from about 1 hr-1 to about 1000 hr-1 and preferablyfrom about 1 hr-1 to about 100 hr-1.

Generally, the process must be carried out at elevated temperatures inorder to form light olefins at a fast enough rate. Thus, the processshould be carried out at a temperature of about 300° C. to about 600°C., preferably from about 400° C. to about 550° C. and most preferablyfrom about 435° C. to about 525° C. The process may be carried out overa wide range of pressure including autogenous pressure. Thus, thepressure can vary from about 0 kPa (0 psig) to about 1724 kPa (250 psig)and preferably from about 34 kPa (5 psig) to about 345 kPa (50 psig).

Optionally, the methanol feedstock may be diluted with an inert diluentin order to more efficiently convert the methanol to olefins. Examplesof the diluents which may be used are helium, argon, nitrogen, carbonmonoxide, carbon dioxide, hydrogen, steam, paraffinic hydrocarbons, e.g., methane, aromatic hydrocarbons, e. g., benzene, toluene and mixturesthereof. The amount of diluent used can vary considerably and is usuallyfrom about 5 to about 90 mole percent of the feedstock and preferablyfrom about 25 to about 75 mole percent.

The actual configuration of the reaction zone may be any well knowncatalyst reaction apparatus known in the art. Thus, a single reactionzone or a number of zones arranged in series or parallel may be used. Insuch reaction zones the methanol feedstock is flowed through a bedcontaining the AlPO-78 catalyst. When multiple reaction zones are used,one or more AlPO-78 catalysts may be used in series to produce thedesired product mixture. Instead of a fixed bed, a dynamic bed system,(e. g., fluidized bed or moving bed), may be used. Such a dynamic systemwould facilitate any regeneration of the AlPO-78 catalyst that may berequired. If regeneration is required, the AlPO-78 catalyst can becontinuously introduced as a moving bed to a regeneration zone where itcan be regenerated by means such as oxidation in an oxygen containingatmosphere to remove carbonaceous materials.

The AlPO-78 materials of this invention can also be used as an adsorbentfor water vapor. The adsorbent may be a component of an adsorption heatpump apparatus. Adsorbents used for adsorption heat pump purposes aredesired to have a high capacity for water vapor, as well as a largecrystallographic density. The crystallographic density of microporouscrystalline materials is conveniently expressed in units of T-atom/1000Å³. Generally speaking, adsorbents with a low density can be problematicsince they would require a large volume of material to take up a givenquantity of adsorbate. This can be troublesome if space is limited inthe application. It is thus of interest to consider uptake capacity on avolumetric basis as opposed to a gravimetric basis.

As measured, AlPO-78 has superior uptake characteristics (on avolumetric basis) to both SAPO-34 and SAPO-5, which are preferredsilicoaluminophosphate materials for use in adsorption heat pumps (seeU.S. Pat. Nos. 7,422,993 and 9,517,942). Thus, AlPO-78 could be apreferred material for use in adsorption heat pumps.

The following examples are presented in illustration of this inventionand are not intended as undue limitations on the generally broad scopeof the invention as set out in the appended claims. The products will bedesignated with names that contain the suffix “-78” to indicate the“-78” structure and prefix that reflects the compositional nature of theproduct, such as “SAPO” for a silicoaluminophosphate, “ZnAPO” for a zincaluminophosphate, and “MgAPSO” for a magnesium silicoaluminophosphate,etc.

The structure of the AlPO-78 compositions of this invention wasdetermined by x-ray analysis. The x-ray patterns presented in thefollowing examples were obtained using standard x-ray powder diffractiontechniques. The radiation source was a high-intensity, x-ray tubeoperated at 45 kV and 35 mA. The diffraction pattern from the copperK-alpha radiation was obtained by appropriate computer based techniques.Flat compressed powder samples were continuously scanned at 2° to 56°(2θ). Interplanar spacings (d) in Angstrom units were obtained from theposition of the diffraction peaks expressed as θ where θ is the Braggangle as observed from digitized data. Intensities were determined fromthe integrated area of diffraction peaks after subtracting background,“I_(o)” being the intensity of the strongest line or peak, and “I” beingthe intensity of each of the other peaks.

As will be understood by those skilled in the art, the determination ofthe parameter 2θ is subject to both human and mechanical error, which incombination can impose an uncertainty of about ±0.4° on each reportedvalue of 2θ. This uncertainty is, of course, also manifested in thereported values of the d-spacings, which are calculated from the 2θvalues. This imprecision is general throughout the art and is notsufficient to preclude the differentiation of the present crystallinematerials from each other and from the compositions of the prior art. Insome of the x-ray patterns reported, the relative intensities of thed-spacings are indicated by the notations vs, s, m, w, and vw whichrepresent very strong, strong, medium, weak, and very weak respectively.In terms of 100×I/I_(o), the above designations are defined as:

vw=0-5; w=5-15; m=15-40: s=40-75 and vs=75-100

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present.

In order to more fully illustrate the invention, the following examplesare set forth. It is to be understood that the examples are only by wayof illustration and are not intended as an undue limitation on the broadscope of the invention as set forth in the appended claims.

EXAMPLE 1

117.03 g of water was weighed into a 500 cc Teflon bottle. 65.43 g of1,4-dibromobutane (99%) was added, and then the mixture was placed intoan ice bath. To the above mixture, 51.6 g of Piperidine (99%) was addedunder magnetic stirring. The water and piperidine combined to form acloudy phase while the denser 1,4-dibromobutane remained on the bottom.The Teflon bottle was placed under an overheard mixer and stirredsomewhat vigorously. After about 5 minutes a clear light yellow templatesolution is formed. The reaction is continued for about 1 hour beforethe stirring is stopped.

EXAMPLE 2

1154 g of the solution from Example 1 was contacted with 355.1 g of Ag₂Oin a round-bottom flask, which combined to form a grey opaque solution.The flask was placed under a high speed overheard stirrer for stirringat room temperature for 1 day. The sample was filtered to remove theprecipitated silver bromide and the final solution was sent for wateranalysis, which showed that the sample was composed of 78.6% water.

EXAMPLE 3

51.85g of the product of Example 2 was combined with 4.56 g of Al(OH)₃(Al=27.9%). 0.48 g of Ludox AS-40 (Sigma-Aldrich) was added to the gelfollowed by 11.77 g phosphoric acid, 85%, which is added very slowly dueto the resulting exotherm. The gel was then stirred vigorously for 2hours. The final gel mixture was distributed equally into 2 45 ccautoclaves and digested for 4 and 5 days at 170° C. Afterwards, the gelswere cooled to room temperature, the products were isolated bycentrifugation, and the solids dried at 100° C. overnight. XRD analysisof the as-synthesized material revealed the following lines:

2-Theta d(Å) Intensity 7.96 11.09 m 8.31 10.63 m 8.87 9.97 s 9.82 9.00vs 10.76 8.21 m 11.80 7.49 m 13.57 6.52 s 14.16 6.25 vs 15.93 5.56 m16.23 5.46 s 16.75 5.29 m 17.34 5.11 s 17.87 4.96 s 18.12 4.89 s 18.824.71 w 19.62 4.52 w 20.86 4.26 s 21.60 4.11 m 22.00 4.04 s 22.26 3.99 s22.67 3.92 m 23.23 3.83 w 23.63 3.76 s 23.93 3.72 w 25.15 3.54 vs 26.253.39 m 26.49 3.36 m 26.94 3.31 m 27.26 3.27 m 28.54 3.13 m 29.54 3.02 m30.99 2.88 w 31.73 2.82 m 32.11 2.79 m 32.55 2.75 w 33.33 2.69 vw 33.772.65 w 35.02 2.56 vw

The products of these syntheses were identified as SAPO-78 by XRD.Elemental analysis gave an observed stoichiometry ofSi_(0.055)AlP_(0.992.)

EXAMPLE 4

The product of Example 3 was calcined in air at 600° C. in a mufflefurnace. The furnace was ramped at 2° C./min to the target temperature.After calcination for 4 hours at 600° C., the sample was cooled to roomtemperature. XRD analysis of the calcined material revealed thefollowing lines:

2-Theta d(Å) Intensity 8.09 10.93 w 8.47 10.44 m 8.69 10.17 m 9.84 8.98s 10.76 8.21 s 12.90 6.86 vw 13.81 6.41 vs 14.08 6.29 m 16.22 5.46 vw16.57 5.35 w 16.99 5.22 vw 17.55 5.06 m 17.87 4.96 s 19.76 4.49 w 20.544.32 w 21.22 4.18 w 21.92 4.05 m 22.39 3.97 m 22.64 3.92 w 24.03 3.70 m24.21 3.67 m 24.69 3.60 s 25.97 3.43 w 26.27 3.39 m 26.61 3.35 m 27.463.25 m 27.82 3.20 m 28.40 3.14 m 28.96 3.08 w 29.54 3.02 w 29.89 2.99 vw30.38 2.94 vw 31.31 2.85 w 31.69 2.82 w 32.34 2.77 w 32.77 2.73 w 33.092.71 m 34.35 2.61 vw 35.30 2.54 m

The surface area of the calcined SAPO-78 (measured by nitrogenadsorption at 77 K) was determined to be 394 m²/g, and the microporevolume was determined to be 0.20 cm³/g.

EXAMPLE 5

134.54 g of the product of Example 2 was combined with 10.94 g ofAl(OH)₃ (Al=27.9%). 11.77 g phosphoric acid, 85%, which is added veryslowly due to resulting exotherm, is stirred in. The gel was then mixedvigorously for 2 hours. The final gel was transferred to a 300 ccstirred autoclave and digested for 5 days at 170° C. at 250 rpm.Afterwards, the gel was cooled to room temperature, the product wasisolated by centrifugation, and the solids dried at 100° C. overnight.XRD analysis of the as-synthesized material revealed the followinglines:

2-Theta d(Å) Intensity 7.91 11.17 m 8.23 10.74 s 8.98 9.84 s 9.77 9.05vs 10.64 8.31 m 10.97 8.06 m 13.34 6.63 s 13.50 6.56 s 14.18 6.24 s14.49 6.11 s 15.59 5.68 m 15.83 5.59 m 16.09 5.50 s 16.63 5.32 m 16.955.23 m 17.29 5.13 s 17.99 4.93 s 18.43 4.81 s 19.13 4.64 w 19.76 4.49 m20.74 4.28 s 21.12 4.20 m 21.72 4.09 m 21.95 4.05 s 22.69 3.92 m 23.393.80 m 23.65 3.76 s 23.83 3.73 m 24.82 3.58 w 25.21 3.53 vs 26.23 3.40 m26.43 3.37 m 26.89 3.31 m 27.18 3.28 m 28.42 3.14 w 28.80 3.10 w 29.323.04 m 30.71 2.91 w 31.25 2.86 m 31.99 2.80 s 32.25 2.77 m 32.81 2.73 m33.25 2.69 w 33.61 2.66 vw 34.92 2.57 vw 35.21 2.55 w

The product of this synthesis was identified as AlPO-78 by XRD.Elemental analysis gave stoichiometry of AlP_(0.992.)

EXAMPLE 6

The product of Example 5 was calcined in air at 600° C. in a mufflefurnace. The furnace was ramped at 2° C/min to the target temperature.After calcination for 4 hours at 600° C., the sample was cooled to roomtemperature. The surface area of the calcined AlPO-78 (measured bynitrogen adsorption at 77 K) was determined to be 392 m²/g, and themicropore volume was determined to be 0.22 cm³/g. XRD analysis of thecalcined material revealed the following lines:

2-Theta d(Å) Intensity 8.05 10.97 w 8.44 10.46 m 8.68 10.18 m 9.82 9.00s 10.74 8.23 m 12.89 6.86 vw 13.76 6.43 vs 14.05 6.30 m 16.20 5.47 vw16.96 5.22 w 17.49 5.07 m 17.84 4.97 m 19.74 4.49 w 20.48 4.33 w 21.304.17 w 21.89 4.06 s 22.30 3.98 s 22.59 3.93 w 24.01 3.70 m 24.67 3.61 m25.96 3.44 w 26.55 3.36 m 27.76 3.21 m 28.46 3.13 m 29.52 3.02 w 31.292.86 vw 31.61 2.83 w 32.33 2.77 w 32.87 2.72 w 35.23 2.55 w

McBain adsorption experiments revealed the following uptake behavior:

Molecule Pressure (torr) Wt. % Uptake H₂O 4.6 25.7 CO₂ 250 3.5 n-C₄H₁₀700 0.4

EXAMPLE 7

115.3 g of the product of Example 2 was combined with 11.15 g of aluminatrihydrate (Al=34.3%), 1.05 g Ludox AS-40, and 25.83 g phosphoric acid,85%, which is added very slowly due to resulting exotherm, is stirredin. The gel was then mixed vigorously for 2 hours. The final gel wastransferred to a 300cc stirred autoclave and digested for 1 day at 100°then 3 days at 160° C. at 150 rpm. Afterwards, the gel was cooled toroom temperature, the product was isolated by centrifugation, and thesolids dried at 100° C. overnight. The product of this synthesis wasidentified as SAPO-78 by XRD. Elemental analysis gave a stoichiometry ofSi_(0.056)AlP_(0.860).

EXAMPLE 8

The product of Example 7 was calcined in air at 600° C. in a mufflefurnace. The furnace was ramped at 2° C./min to the target temperature.After calcination for 4 hours at 600° C., the sample was cooled to roomtemperature. The surface area of the calcined SAPO-78 (measured bynitrogen adsorption at 77 K) was determined to be 417 m²/g, and themicropore volume was determined to be 0.21 cm³/g.

COMPARATIVE EXAMPLE 1

SAPO-34 was synthesized following Example 35 of U.S. Pat. No. 4,440,871,incorporated herein by reference. After the as-synthesized SAPO-34 wasisolated from the mother liquor and dried, it was calcined at 600° C.for 4 hours in air. XRD analysis of the calcined material showed thatthe product was pure SAPO-34.

COMPARATIVE EXAMPLE 2

SAPO-5 was synthesized following Example 12 of U.S. Pat. No. 4,440,871,incorporated by reference. After the as-synthesized SAPO-5 was isolatedfrom the mother liquor and dried, it was calcined at 600° C. for 4 hoursin air. XRD analysis of the calcined material showed that the productwas pure SAPO-5.

EXAMPLE 9

The products of Example 6, Example 8, Comparative Example 1, andComparative Example 2 were tested for water vapor adsorption in a McBaingravimetric balance. Prior to water vapor adsorption, the materialsheated at 400° C. under vacuum. Water adsorption isotherms were recordedfor each material at 25° C., and are displayed in FIG. 2. Saturationcapacities were measured in terms of mass %, then converted to volume %using the crystal density of each framework, which is determined fromthe unit cell of each material. The results are displayed in Table 9:

Saturation Capacity Crystal Density Volumetric Capacity Material (mass%) (g/mL) (volume %) AlPO-78 29.7 1.70 50.5 SAPO-78 28.3 1.70 48.1SAPO-34 31.0 1.43 44.3 SAPO-5 20.3 1.75 35.6

It is seen that both AlPO-78 and SAPO-78 have superior volumetriccapacity for water vapor over the comparative examples SAPO-34 andSAPO-5.

Specific Embodiments

While the following is described in conjunction with specificembodiments, it will be understood that this description is intended toillustrate and not limit the scope of the preceding description and theappended claims.

A first embodiment of the invention is a microporous crystallinematerial that has an empirical composition in an as-synthesized form andon an anhydrous basis expressed by an empirical formula R⁺ _(r)M_(m)²⁺EP_(x)Si_(y)O_(z) where M is at least one framework divalent cationand is selected from the group consisting of alkaline earth andtransition metals, wherein M is a cation selected from the groupconsisting of beryllium, magnesium, cobalt (II), manganese, zinc, iron(II), nickel and mixtures thereof. R is an organoammonium cation, “r” isthe mole ratio of R to E and varies from about 0.1 to about 2.0, “m” isthe mole ratio of M to E and varies from 0 to about 1.0, “x” is a moleratio of P to E and varies from 0.5 to about 2.0, a ratio of silicon toE is represented by “y” which varies from about 0 to about 1.0, E is atrivalent element which is tetrahedrally coordinated, is present in theframework, and is selected from the group consisting of aluminum,gallium, iron (III) and boron and “z” is a mole ratio of O to E and isgiven by an equation z=(2·m+r+3+5·x+4·y)/2 and is characterized by afollowing x-ray diffraction pattern, having at least the d-spacings andrelative intensities set forth in Table 1.

TABLE 1 2-Theta d(Å) Intensity 7.88-7.98 11.21-11.07 m-s 8.15-8.5010.84-10.39 m-s 8.82-9.05 10.01-9.76  s 9.67-9.96 9.14-8.87 s-vs10.58-10.81 8.35-8.17 m 10.92-11.71 8.09-7.55 m-s 13.21-13.67 6.69-6.47s 14.10-14.54 6.27-6.08 s-vs 15.48-16.02 5.72-5.53 m 16.05-16.245.52-5.45 s 16.44-16.81 5.39-5.28 m 16.87-17.01 5.25-5.21 m-s17.19-17.43 5.15-5.08 s 17.78-18.46 4.98-4.80 s-vs 18.73-19.22 4.73-4.61vw-w 19.48-19.86 4.55-4.47 w-m 20.47-20.96 4.33-4.23 s 21.00-21.454.23-4.14 m-s 21.52-21.73 4.12-4.08 m-s 21.88-22.10 4.06-4.02 s22.15-22.42 4.01-3.96 m-s 22.52-22.95 3.94-3.87 w-m 23.14-23.523.84-3.78 w-m 23.58-23.71 3.77-3.75 s 23.75-24.01 3.74-3.70 w-m24.75-24.93 3.59-3.57 w-m 25.01-25.47 3.56-3.49 vs 26.15-26.31 3.40-3.38w-m 26.37-26.54 3.38-3.35 m 26.78-27.02 3.33-3.30 w-m 27.11-27.403.29-3.25 m 28.39-28.86 3.14-3.09 w-m 29.22-29.65 3.05-3.01 m30.60-30.95 2.92-2.89 w-m 31.62-31.93 2.83-2.80 w-m 31.97-32.282.80-2.77 w-s 32.44-32.89 2.76-2.72 w-m 33.19-33.40 2.70-2.68 vw-w33.51-33.82 2.67-2.65 w-m 34.72-35.08 2.58-2.55 vw-w

An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the first embodiment in this paragraphwherein after being calcined, the AlPO-78 material is characterized bythe x-ray diffraction pattern, having at least the d-spacings andrelative intensities set forth in Table 2 below.

TABLE 2 2-Theta d(Å) Intensity 8.02-8.12 11.01-10.88 w 8.40-8.5110.51-10.38 m 8.63-8.73 10.23-10.12 w-m 9.78-9.89 9.03-8.93 m-s10.70-10.81 8.26-8.17 m-s 12.83-12.95 6.89-6.82 vw 13.71-13.86 6.45-6.38vs 14.00-14.13 6.32-6.26 m-s 16.16-16.64 5.48-5.32 vw-w 16.92-17.055.23-5.19 vw-w 17.44-17.56 5.08-5.04 m 17.79-17.93 4.98-4.94 m-s19.68-19.89 4.51-4.46 w 20.43-20.61 4.34-4.30 w-m 21.17-21.35 4.19-4.16w-m 21.81-21.99 4.07-4.04 m-s 22.15-22.53 4.01-3.94 m-s 22.55-22.743.94-3.91 w-m 23.95-24.25 3.71-3.67 m-s 24.57-24.79 3.62-3.59 m-s25.87-26.31 3.44-3.38 w-m 26.49-26.71 3.36-3.33 m 27.40-27.88 3.25-3.20m-s 28.32-28.52 3.15-3.13 m-s 28.85-29.02 3.09-3.07 vw-w 29.40-29.633.03-3.01 w-m 29.71-29.93 3.00-2.98 vw 30.28-30.44 2.95-2.93 vw-w31.21-31.38 2.86-2.85 vw-w 32.18-32.50 2.79-2.75 w-m 32.65-32.922.74-2.72 w-m 33.00-33.15 2.71-2.70 w-m 34.25-34.41 2.61-2.60 vw-w35.16-35.35 2.55-2.54 w-m

An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the first embodiment in this paragraphwherein the microporous crystalline material is characterized on ananhydrous basis by the empirical formula H_(w)M_(m) ²⁺EP_(x)Si_(y)O_(z)where M is at least one metal cation of valence +2 selected from thegroup consisting of Be²⁺, Mg²⁺, Zn²⁺, Co²⁺, Mn²⁺, Fe²⁺, Ni²⁺, “m” is themole ratio of M to E and varies from 0 to about 1.0, H is a proton, w”is the mole ratio of H to E and varies from 0 to 2.5, E is a trivalentelement selected from the group consisting of aluminum, gallium, iron,boron and mixtures thereof, “x” is mole ratio of P to E and varies from0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0.05to about 1.0, “m”+“y”≥0.1, and “z” is the mole ratio of O to E and has avalue determined by the equation z=(w+2·m+3+5·x+4·y)/2. An embodiment ofthe invention is one, any or all of prior embodiments in this paragraphup through the first embodiment in this paragraph wherein themicroporous crystalline material indexes on a unit cell with hexagonalaxes with lattice parameters a=12.768 Å and c=60.825 Å and has an ABC-6net structure with the stacking sequence repeating every 24 layers alongthe c-axis (p=60.825/2.5=24.33).

A second embodiment of the invention is a method of making a AlPO-78microporous crystalline material comprising preparing a reaction mixturecontaining reactive sources described in terms of molar ratios of theoxides by a formula aR₂O bMO E₂O₃ cP₂O₅ dSiO₂ eH₂O where “a” varies fromabout 0.75 to about 16, “b” varies from about 0 to about 2, “c” variesfrom about 0.8 to about 8, “d” varies from about 0 to about 4, and “e”varies from 30 to 800 wherein reactive sources of R, E, phosphorus andone or both M and silicon; reacting the reaction mixture at atemperature from about 60° C. to about 200° C. for a period of about 1day to about 21 days; and isolating a solid product from a heterogeneousmixture wherein the AlPO-78 microporous material, is characterized bythe x-ray following diffraction pattern, having at least the d-spacingsand relative intensities set forth in Table 1.

TABLE 1 2-Theta d(Å) Intensity 7.88-7.98 11.21-11.07 m-s 8.15-8.5010.84-10.39 m-s 8.82-9.05 10.01-9.76  s 9.67-9.96 9.14-8.87 s-vs10.58-10.81 8.35-8.17 m 10.92-11.71 8.09-7.55 m-s 13.21-13.67 6.69-6.47s 14.10-14.54 6.27-6.08 s-vs 15.48-16.02 5.72-5.53 m 16.05-16.245.52-5.45 s 16.44-16.81 5.39-5.28 m 16.87-17.01 5.25-5.21 m-s17.19-17.43 5.15-5.08 s 17.78-18.46 4.98-4.80 s-vs 18.73-19.22 4.73-4.61vw-w 19.48-19.86 4.55-4.47 w-m 20.47-20.96 4.33-4.23 s 21.00-21.454.23-4.14 m-s 21.52-21.73 4.12-4.08 m-s 21.88-22.10 4.06-4.02 s22.15-22.42 4.01-3.96 m-s 22.52-22.95 3.94-3.87 w-m 23.14-23.523.84-3.78 w-m 23.58-23.71 3.77-3.75 s 23.75-24.01 3.74-3.70 w-m24.75-24.93 3.59-3.57 w-m 25.01-25.47 3.56-3.49 vs 26.15-26.31 3.40-3.38w-m 26.37-26.54 3.38-3.35 m 26.78-27.02 3.33-3.30 w-m 27.11-27.403.29-3.25 m 28.39-28.86 3.14-3.09 w-m 29.22-29.65 3.05-3.01 m30.60-30.95 2.92-2.89 w-m 31.62-31.93 2.83-2.80 w-m 31.97-32.282.80-2.77 w-s 32.44-32.89 2.76-2.72 w-m 33.19-33.40 2.70-2.68 vw-w33.51-33.82 2.67-2.65 w-m 34.72-35.08 2.58-2.55 vw-w

An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the first embodiment in this paragraphwherein the AlPO-78 is calcined at a temperature of at least 550° C. andis characterized by the x-ray diffraction pattern, having at least thed-spacings and relative intensities set forth in Table 2 below.

TABLE 2 2-Theta d(Å) Intensity 8.02-8.12 11.01-10.88 w 8.40-8.5110.51-10.38 m 8.63-8.73 10.23-10.12 w-m 9.78-9.89 9.03-8.93 m-s10.70-10.81 8.26-8.17 m-s 12.83-12.95 6.89-6.82 vw 13.71-13.86 6.45-6.38vs 14.00-14.13 6.32-6.26 m-s 16.16-16.64 5.48-5.32 vw-w 16.92-17.055.23-5.19 vw-w 17.44-17.56 5.08-5.04 m 17.79-17.93 4.98-4.94 m-s19.68-19.89 4.51-4.46 w 20.43-20.61 4.34-4.30 w-m 21.17-21.35 4.19-4.16w-m 21.81-21.99 4.07-4.04 m-s 22.15-22.53 4.01-3.94 m-s 22.55-22.743.94-3.91 w-m 23.95-24.25 3.71-3.67 m-s 24.57-24.79 3.62-3.59 m-s25.87-26.31 3.44-3.38 w-m 26.49-26.71 3.36-3.33 m 27.40-27.88 3.25-3.20m-s 28.32-28.52 3.15-3.13 m-s 28.85-29.02 3.09-3.07 vw-w 29.40-29.633.03-3.01 w-m 29.71-29.93 3.00-2.98 vw 30.28-30.44 2.95-2.93 vw-w31.21-31.38 2.86-2.85 vw-w 32.18-32.50 2.79-2.75 w-m 32.65-32.922.74-2.72 w-m 33.00-33.15 2.71-2.70 w-m 34.25-34.41 2.61-2.60 vw-w35.16-35.35 2.55-2.54 w-m

An embodiment of the invention is one, any or all prior embodiments inthis paragraph up through the first embodiment in this paragraph whereinthe sources of aluminum are selected from the group consisting ofaluminum alkoxides, precipitated aluminas, aluminum metal, aluminumhydroxide, aluminum salts and alumina sols. An embodiment of theinvention is one, any or all prior embodiments in this paragraph upthrough the first embodiment in this paragraph wherein sources ofphosphorus are selected from the group consisting of orthophosphoricacid, phosphorus pentoxide, and ammonium dihydrogen phosphate. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the first embodiment in this paragraph whereinsources of silica are selected from the group consisting oftetraethylorthosilicate, colloidal silica, and precipitated silica. Anembodiment of the invention is one, any or all prior embodiments in thisparagraph up through the first embodiment in this paragraph whereinsources of E elements are selected from the group consisting oforganoammonium borates, boric acid, precipitated gallium oxyhydroxide,gallium sulfate, ferric sulfate, and ferric chloride. An embodiment ofthe invention is one, any or all prior embodiments in this paragraph upthrough the first embodiment in this paragraph wherein sources of the Mmetals are selected from the group consisting of halide salts, nitratesalts, acetate salts, and sulfate salts of the respective alkaline earthand transition metals. An embodiment of the invention is one, any or allof prior embodiments in this paragraph up through the first embodimentin this paragraph wherein R is an organoammonium cation prepared from areaction of an aqueous mixture of a cyclic secondary amine and anorganic dihalide. An embodiment of the invention is one, any or allprior embodiments in this paragraph up through the first embodiment inthis paragraph wherein the cyclic secondary amines are selected from thegroup consisting of piperidine, homopiperidine, pyrrolidine, andmorpholine. An embodiment of the invention is one, any or all of priorembodiments in this paragraph up through the first embodiment in thisparagraph wherein the AlPO-78 microporous crystalline material iscalcined at a temperature of at least 600° C.

A third embodiment of the invention is a process of separating mixturesof molecular species, removing contaminants or catalyzing hydrocarbonconversion processes comprising contacting a feed stream with amicroporous crystalline material that has an empirical composition in acalcined form and on an anhydrous basis expressed by an empiricalformula R⁻ _(r)M_(m) ²⁺EP_(x)Si_(y)O_(z) where M is at least oneframework divalent cation and is selected from the group consisting ofalkaline earth and transition metals, wherein M is a cation selectedfrom the group consisting of beryllium, magnesium, cobalt (II),manganese, zinc, iron (II), nickel and mixtures thereof. R is anorganoammonium cation, “r” is the mole ratio of R to E and varies fromabout 0.1 to about 2.0, “m” is the mole ratio of M to E and varies from0 to about 1.0, “x” is a mole ratio of P to E and varies from 0.5 toabout 2.0, a ratio of silicon to E is represented by “y” which variesfrom about 0 to about 1.0, E is a trivalent element which istetrahedrally coordinated, is present in the framework, and is selectedfrom the group consisting of aluminum, gallium, iron (III) and boron and“z” is a mole ratio of O to E and is given by an equationz=(2·m+r+3+5·x+4y)/2 and is characterized by an x-ray followingdiffraction pattern, having at least the d-spacings and relativeintensities set forth in Table 2.

TABLE 2 2-Theta d(Å) Intensity 8.02-8.12 11.01-10.88 w 8.40-8.5110.51-10.38 m 8.63-8.73 10.23-10.12 w-m 9.78-9.89 9.03-8.93 m-s10.70-10.81 8.26-8.17 m-s 12.83-12.95 6.89-6.82 vw 13.71-13.86 6.45-6.38vs 14.00-14.13 6.32-6.26 m-s 16.16-16.64 5.48-5.32 vw-w 16.92-17.055.23-5.19 vw-w 17.44-17.56 5.08-5.04 m 17.79-17.93 4.98-4.94 m-s19.68-19.89 4.51-4.46 w 20.43-20.61 4.34-4.30 w-m 21.17-21.35 4.19-4.16w-m 21.81-21.99 4.07-4.04 m-s 22.15-22.53 4.01-3.94 m-s 22.55-22.743.94-3.91 w-m 23.95-24.25 3.71-3.67 m-s 24.57-24.79 3.62-3.59 m-s25.87-26.31 3.44-3.38 w-m 26.49-26.71 3.36-3.33 m 27.40-27.88 3.25-3.20m-s 28.32-28.52 3.15-3.13 m-s 28.85-29.02 3.09-3.07 vw-w 29.40-29.633.03-3.01 w-m 29.71-29.93 3.00-2.98 vw 30.28-30.44 2.95-2.93 vw-w31.21-31.38 2.86-2.85 vw-w 32.18-32.50 2.79-2.75 w-m 32.65-32.922.74-2.72 w-m 33.00-33.15 2.71-2.70 w-m 34.25-34.41 2.61-2.60 vw-w35.16-35.35 2.55-2.54 w-m

An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the second embodiment in this paragraphwherein the separation of molecular species is in an operation of anadsorption heat pump wherein water vapor is adsorbed by the microporouscrystalline material. An embodiment of the invention is one, any or allof prior embodiments in this paragraph up through the second embodimentin this paragraph wherein the hydrocarbon conversion processes areselected from the group consisting of cracking, hydrocracking,alkylation of both aromatics and isoparaffin, isomerization,polymerization, reforming, hydrogenation, dehydrogenation,transalkylation, dealkylation, hydration, dehydration, hydrotreating,hydrodenitrogenation, hydrodesulfurization, methanol to olefins,methanation and a syngas shift process. An embodiment of the inventionis one, any or all prior embodiments in this paragraph up through theembodiment in this paragraph wherein the separation of molecular speciesis based on the molecular size (kinetic diameter) or on the degree ofpolarity of the molecular species.

1. A microporous crystalline material that has an empirical compositionin an as-synthesized form and on an anhydrous basis expressed by anempirical formula:R⁺ _(r)M_(m) ²⁺EP_(x)Si_(y)O_(z) where M is at least one frameworkdivalent cation and is selected from the group consisting of alkalineearth and transition metals, wherein M is a cation selected from thegroup consisting of beryllium, magnesium, cobalt (II), manganese, zinc,iron (II), nickel and mixtures thereof. R is an organoammonium cation,“r” is the mole ratio of R to E and varies from about 0.1 to about 2.0,“m” is the mole ratio of M to E and varies from 0 to about 1.0, “x” is amole ratio of P to E and varies from 0.5 to about 2.0, a ratio ofsilicon to E is represented by “y” which varies from about 0 to about1.0, E is a trivalent element which is tetrahedrally coordinated, ispresent in the framework, and is selected from the group consisting ofaluminum, gallium, iron (III) and boron and “z” is a mole ratio of O toE and is given by an equation:z=(2·m+r+3+5·x+4·y)/2 and is characterized by a following x-raydiffraction pattern, having at least the d-spacings and relativeintensities set forth in Table 1: TABLE 1 2-Theta d(Å) Intensity7.88-7.98 11.21-11.07 m-s 8.15-8.50 10.84-10.39 m-s 8.82-9.0510.01-9.76  s 9.67-9.96 9.14-8.87 s-vs 10.58-10.81 8.35-8.17 m10.92-11.71 8.09-7.55 m-s 13.21-13.67 6.69-6.47 s 14.10-14.54 6.27-6.08s-vs 15.48-16.02 5.72-5.53 m 16.05-16.24 5.52-5.45 s 16.44-16.815.39-5.28 m 16.87-17.01 5.25-5.21 m-s 17.19-17.43 5.15-5.08 s17.78-18.46 4.98-4.80 s-vs 18.73-19.22 4.73-4.61 vw-w 19.48-19.864.55-4.47 w-m 20.47-20.96 4.33-4.23 s 21.00-21.45 4.23-4.14 m-s21.52-21.73 4.12-4.08 m-s 21.88-22.10 4.06-4.02 s 22.15-22.42 4.01-3.96m-s 22.52-22.95 3.94-3.87 w-m 23.14-23.52 3.84-3.78 w-m 23.58-23.713.77-3.75 s 23.75-24.01 3.74-3.70 w-m 24.75-24.93 3.59-3.57 w-m25.01-25.47 3.56-3.49 vs 26.15-26.31 3.40-3.38 w-m 26.37-26.54 3.38-3.35m 26.78-27.02 3.33-3.30 w-m 27.11-27.40 3.29-3.25 m 28.39-28.863.14-3.09 w-m 29.22-29.65 3.05-3.01 m 30.60-30.95 2.92-2.89 w-m31.62-31.93 2.83-2.80 w-m 31.97-32.28 2.80-2.77 w-s 32.44-32.892.76-2.72 w-m 33.19-33.40 2.70-2.68 vw-w 33.51-33.82 2.67-2.65 w-m34.72-35.08 2.58-2.55 vw-w


2. The microporous crystalline material of claim 1 wherein after beingcalcined said AlPO-78 material is characterized by the x-ray diffractionpattern, having at least the d-spacings and relative intensities setforth in Table 2 below: TABLE 2 2-Theta d(Å) Intensity 8.02-8.1211.01-10.88 w 8.40-8.51 10.51-10.38 m 8.63-8.73 10.23-10.12 w-m9.78-9.89 9.03-8.93 m-s 10.70-10.81 8.26-8.17 m-s 12.83-12.95 6.89-6.82vw 13.71-13.86 6.45-6.38 vs 14.00-14.13 6.32-6.26 m-s 16.16-16.645.48-5.32 vw-w 16.92-17.05 5.23-5.19 vw-w 17.44-17.56 5.08-5.04 m17.79-17.93 4.98-4.94 m-s 19.68-19.89 4.51-4.46 w 20.43-20.61 4.34-4.30w-m 21.17-21.35 4.19-4.16 w-m 21.81-21.99 4.07-4.04 m-s 22.15-22.534.01-3.94 m-s 22.55-22.74 3.94-3.91 w-m 23.95-24.25 3.71-3.67 m-s24.57-24.79 3.62-3.59 m-s 25.87-26.31 3.44-3.38 w-m 26.49-26.713.36-3.33 m 27.40-27.88 3.25-3.20 m-s 28.32-28.52 3.15-3.13 m-s28.85-29.02 3.09-3.07 vw-w 29.40-29.63 3.03-3.01 w-m 29.71-29.933.00-2.98 vw 30.28-30.44 2.95-2.93 vw-w 31.21-31.38 2.86-2.85 vw-w32.18-32.50 2.79-2.75 w-m 32.65-32.92 2.74-2.72 w-m 33.00-33.152.71-2.70 w-m 34.25-34.41 2.61-2.60 vw-w 35.16-35.35 2.55-2.54 w-m


3. The microporous crystalline material of claim 1 characterized on ananhydrous basis by the empirical formula:H_(w)M_(m) ²⁺EP_(x)Si_(y)O_(z) where M is at least one metal cation ofvalence +2 selected from the group consisting of Be²⁺, Mg²⁺, Zn²⁺, Co²⁺,Mn²⁺, Fe²⁺, Ni²⁺, “m” is the mole ratio of M to E and varies from 0 toabout 1.0, H is a proton, w” is the mole ratio of H to E and varies from0 to 2.5, E is a trivalent element selected from the group consisting ofaluminum, gallium, iron, boron and mixtures thereof, “x” is mole ratioof P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Sito E and varies from 0.05 to about 1.0, “m”+“y”≥0.1, and “z” is the moleratio of O to E and has a value determined by the equation:z=(w+2·m+3+5·x+4·y)/2.
 4. The microporous crystalline material of claim1 that indexes on a unit cell with hexagonal axes with latticeparameters a=12.768 Å and c=60.825 Å and has an ABC-6 net structure withthe stacking sequence repeating every 24 layers along the c-axis(p=60.825/2.5=24.33).
 5. A method of making a AlPO-78 microporouscrystalline material comprising preparing a reaction mixture containingreactive sources described in terms of molar ratios of the oxides by aformula:aR₂O:bMO:E₂O₃:cP₂O₅:dSiO₂:eH₂O where “a” varies from about 0.75 to about16, “b” varies from about 0 to about 2, “c” varies from about 0.8 toabout 8, “d” varies from about 0 to about 4, and “e” varies from 30 to800 wherein reactive sources of R, E, phosphorus and one or both M andsilicon; reacting the reaction mixture at a temperature from about 60°C. to about 200° C. for a period of about 1 day to about 21 days; andisolating a solid product from a heterogeneous mixture wherein theAlPO-78 microporous material, is characterized by the x-ray followingdiffraction pattern, having at least the d-spacings and relativeintensities set forth in Table 1: TABLE 1 2-Theta d(Å) Intensity7.88-7.98 11.21-11.07 m-s 8.15-8.50 10.84-10.39 m-s 8.82-9.0510.01-9.76  s 9.67-9.96 9.14-8.87 s-vs 10.58-10.81 8.35-8.17 m10.92-11.71 8.09-7.55 m-s 13.21-13.67 6.69-6.47 s 14.10-14.54 6.27-6.08s-vs 15.48-16.02 5.72-5.53 m 16.05-16.24 5.52-5.45 s 16.44-16.815.39-5.28 m 16.87-17.01 5.25-5.21 m-s 17.19-17.43 5.15-5.08 s17.78-18.46 4.98-4.80 s-vs 18.73-19.22 4.73-4.61 vw-w 19.48-19.864.55-4.47 w-m 20.47-20.96 4.33-4.23 s 21.00-21.45 4.23-4.14 m-s21.52-21.73 4.12-4.08 m-s 21.88-22.10 4.06-4.02 s 22.15-22.42 4.01-3.96m-s 22.52-22.95 3.94-3.87 w-m 23.14-23.52 3.84-3.78 w-m 23.58-23.713.77-3.75 s 23.75-24.01 3.74-3.70 w-m 24.75-24.93 3.59-3.57 w-m25.01-25.47 3.56-3.49 vs 26.15-26.31 3.40-3.38 w-m 26.37-26.54 3.38-3.35m 26.78-27.02 3.33-3.30 w-m 27.11-27.40 3.29-3.25 m 28.39-28.863.14-3.09 w-m 29.22-29.65 3.05-3.01 m 30.60-30.95 2.92-2.89 w-m31.62-31.93 2.83-2.80 w-m 31.97-32.28 2.80-2.77 w-s 32.44-32.892.76-2.72 w-m 33.19-33.40 2.70-2.68 vw-w 33.51-33.82 2.67-2.65 w-m34.72-35.08 2.58-2.55 vw-w


6. The method of claim 5 wherein the AlPO-78 is calcined at atemperature of at least 550° C. and is characterized by the x-raydiffraction pattern, having at least the d-spacings and relativeintensities set forth in Table 2 below: TABLE 2 2-Theta d(Å) Intensity8.02-8.12 11.01-10.88 w 8.40-8.51 10.51-10.38 m 8.63-8.73 10.23-10.12w-m 9.78-9.89 9.03-8.93 m-s 10.70-10.81 8.26-8.17 m-s 12.83-12.956.89-6.82 vw 13.71-13.86 6.45-6.38 vs 14.00-14.13 6.32-6.26 m-s16.16-16.64 5.48-5.32 vw-w 16.92-17.05 5.23-5.19 vw-w 17.44-17.565.08-5.04 m 17.79-17.93 4.98-4.94 m-s 19.68-19.89 4.51-4.46 w20.43-20.61 4.34-4.30 w-m 21.17-21.35 4.19-4.16 w-m 21.81-21.994.07-4.04 m-s 22.15-22.53 4.01-3.94 m-s 22.55-22.74 3.94-3.91 w-m23.95-24.25 3.71-3.67 m-s 24.57-24.79 3.62-3.59 m-s 25.87-26.313.44-3.38 w-m 26.49-26.71 3.36-3.33 m 27.40-27.88 3.25-3.20 m-s28.32-28.52 3.15-3.13 m-s 28.85-29.02 3.09-3.07 vw-w 29.40-29.633.03-3.01 w-m 29.71-29.93 3.00-2.98 vw 30.28-30.44 2.95-2.93 vw-w31.21-31.38 2.86-2.85 vw-w 32.18-32.50 2.79-2.75 w-m 32.65-32.922.74-2.72 w-m 33.00-33.15 2.71-2.70 w-m 34.25-34.41 2.61-2.60 vw-w35.16-35.35 2.55-2.54 w-m


7. The method of claim 5 wherein the sources of aluminum are selectedfrom the group consisting of aluminum alkoxides, precipitated aluminas,aluminum metal, aluminum hydroxide, aluminum salts and alumina sols. 8.The method of claim 5 wherein sources of phosphorus are selected fromthe group consisting of orthophosphoric acid, phosphorus pentoxide, andammonium dihydrogen phosphate.
 9. The method of claim 5 wherein sourcesof silica are selected from the group consisting oftetraethylorthosilicate, colloidal silica, and precipitated silica. 10.The method of claim 5 wherein sources of E elements are selected fromthe group consisting of organoammonium borates, boric acid, precipitatedgallium oxyhydroxide, gallium sulfate, ferric sulfate, and ferricchloride.
 11. The method of claim 5 wherein sources of the M metals areselected from the group consisting of halide salts, nitrate salts,acetate salts, and sulfate salts of the respective alkaline earth andtransition metals.
 12. The method of claim 5 wherein R is anorganoammonium cation prepared from a reaction of an aqueous mixture ofa cyclic secondary amine and an organic dihalide.
 13. The method ofclaim 12 wherein the cyclic secondary amines are selected from the groupconsisting of piperidine, homopiperidine, pyrrolidine, and morpholine.14. The method of claim 6 wherein the AlPO-78 microporous crystallinematerial is calcined at a temperature of at least 600° C.
 15. A processof separating mixtures of molecular species, removing contaminants orcatalyzing hydrocarbon conversion processes comprising contacting a feedstream with a microporous crystalline material that has an empiricalcomposition in a calcined form and on an anhydrous basis expressed by anempirical formula:R⁺ _(r)M_(m) ²⁺EP_(x)Si_(y)O_(z) where M is at least one frameworkdivalent cation and is selected from the group consisting of alkalineearth and transition metals, wherein M is a cation selected from thegroup consisting of beryllium, magnesium, cobalt (II), manganese, zinc,iron (II), nickel and mixtures thereof. R is an organoammonium cation,“r” is the mole ratio of R to E and varies from about 0.1 to about 2.0,“m” is the mole ratio of M to E and varies from 0 to about 1.0, “x” is amole ratio of P to E and varies from 0.5 to about 2.0, a ratio ofsilicon to E is represented by “y” which varies from about 0 to about1.0, E is a trivalent element which is tetrahedrally coordinated, ispresent in the framework, and is selected from the group consisting ofaluminum, gallium, iron (III) and boron and “z” is a mole ratio of O toE and is given by an equation:z=(2·m+r+3+5·x+4·y)/2 and is characterized by an x-ray followingdiffraction pattern, having at least the d-spacings and relativeintensities set forth in Table 2: TABLE 2 2-Theta d(Å) Intensity8.02-8.12 11.01-10.88 w 8.40-8.51 10.51-10.38 m 8.63-8.73 10.23-10.12w-m 9.78-9.89 9.03-8.93 m-s 10.70-10.81 8.26-8.17 m-s 12.83-12.956.89-6.82 vw 13.71-13.86 6.45-6.38 vs 14.00-14.13 6.32-6.26 m-s16.16-16.64 5.48-5.32 vw-w 16.92-17.05 5.23-5.19 vw-w 17.44-17.565.08-5.04 m 17.79-17.93 4.98-4.94 m-s 19.68-19.89 4.51-4.46 w20.43-20.61 4.34-4.30 w-m 21.17-21.35 4.19-4.16 w-m 21.81-21.994.07-4.04 m-s 22.15-22.53 4.01-3.94 m-s 22.55-22.74 3.94-3.91 w-m23.95-24.25 3.71-3.67 m-s 24.57-24.79 3.62-3.59 m-s 25.87-26.313.44-3.38 w-m 26.49-26.71 3.36-3.33 m 27.40-27.88 3.25-3.20 m-s28.32-28.52 3.15-3.13 m-s 28.85-29.02 3.09-3.07 vw-w 29.40-29.633.03-3.01 w-m 29.71-29.93 3.00-2.98 vw 30.28-30.44 2.95-2.93 vw-w31.21-31.38 2.86-2.85 vw-w 32.18-32.50 2.79-2.75 w-m 32.65-32.922.74-2.72 w-m 33.00-33.15 2.71-2.70 w-m 34.25-34.41 2.61-2.60 vw-w35.16-35.35 2.55-2.54 w-m


16. The process of claim 15 wherein the separation of molecular speciesis in an operation of an adsorption heat pump wherein water vapor isadsorbed by said microporous crystalline material.
 17. The process ofclaim 15 wherein said hydrocarbon conversion processes are selected fromthe group consisting of cracking, hydrocracking, alkylation of botharomatics and isoparaffin, isomerization, polymerization, reforming,hydrogenation, dehydrogenation, transalkylation, dealkylation,hydration, dehydration, hydrotreating, hydrodenitrogenation,hydrodesulfurization, methanol to olefins, methanation and a syngasshift process.
 18. The process of claim 15 wherein said separation ofmolecular species is based on the molecular size (kinetic diameter) oron the degree of polarity of the molecular species.